Theoretical study of solvent effect on elimination reactions:
hybrid-DFT study, and NBO analysis
- Received: November, 25, 2023
- Revised: January, 16, 2024
- Accepted for publication: January, 16, 2024
- DOI 10.26902/JSC_id126617
- EDN: WQVSQE
- Views: 123
Department of Chemistry, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran
In elimination reactions, the arrangement of leaving groups plays a crucial role in facilitating the reaction. On the other hand, equatorial and axial stereoisomers of a compound have a different share of stability. The presence of a solvent plays a different role in the stability of each stereoisomer. From LC-wPBE and B3LYP methods and natural bond orbital (NBO) interpretation to investigate 3-chloro-8-methyl-8-azabicyclo [3.2.1] octane (1), 3-bromo-8-methyl-8-azabicyclo [3.2.1] octane (2), and 8-methyl-8-azabicyclo [3.2.1] octan-3-yl 4-methylbenzenesulfonate (3), was used. Investigation of thermodynamic parameters showed that equatorial stereoisomers are more stable than axial stereoisomers, and by changing the gas phase to n-hexane and water, the stability of equatorial stereoisomers increased. The stability of the equatorial stereoisomers is the result of the electrostatic model involving dipole–dipole interactions and the combined effects of hyperconjugation interactions and total steric exchange energy (TSEE). Therefore, it can be expressed that the equatorial stereoisomers of compounds 1–3 show superior performance in the elimination reaction of 1, 4 in the presence of
a solvent, and this performance becomes more evident by changing the polarity
of the solvent.
Keywords: anomeric effect, hybrid-DFT, natural bond orbital (NBO), total steric exchange energy (TSEE)
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Импакт-фактор 2023 1.2 |
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Срок опубликования 4 мес |
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